Azo dyestuffs



AZO DYESTUFFS Reinhard Neier and Walter Wehrli, Basel, Switzerland, assignors to Sandoz A. G., Basel, Switzerland, a Swiss firm No Drawing. Application February 11, 1952, Serial No. 271,064

Claims priority, application Switzerland February 17, 1951 7 Claims. (Cl. 260-145) The present invention relates to valuable dyestutls Which represent the combination of, on the one hand, a

diazo or tetrazo compound from an amine or diamine of the formula i G] XTNOC Y n (I) wherein X stands for a radical of the benzene or naphthalene series which may optionally carry an azo substituent, one Y stands for the NHz group, the other Y stands for a carboxyl group or an esterified carboxyl group, Z stands for hydrogen or an alkyl or aryl group, and n represents one of the integers 1 and 2, with, on the other hand, a compound containing a couplable methylene group or a hydroxybenzene or hydroxynaphthalene which couples in ortho-position to the azo group.

In order to prepare the amine or diamine of Composition (I), supra, the appropriate acid chloride corresponding to the formula a l (II) wherein one A stands for --NO2 and the other A stands for -COO-1ower alkyl, are employed. These acid chlorides may be prepared from the corresponding carboxylic acids, for example by the action of phosphorus pentachloride or thionyl chloride.

The acid chloride is reacted in aqueous solution or in an anhydrous solvent with the appropriate primary or secondary amine, preferably with an addition of an acidbinding agent such as sodium acetate, sodium carbonate, calcium carbonate or magnesium oxide or a tertiary base such as N-dimethylaminobenzene or pyridine. Saponification of the ester group of the thus-obtained acid amide and reduction of the nitro group to the amino group results in the initially-mentioned amine or diamine. Alternatively, the ester group may be saponified after the said reduction or only in the dyestufi itself. In those cases where, as hereinafter set forth, the metal complex of the dyestufi is prepared in substance, a separate saponification of the ester group is unnecessary, since it splits ofi readily during the metallization, as for example when the latter is a coppering carried out in a sodium acetate fusion.

Suitable for reaction with the acid chlorides, according to this invention, are the primary and secondary monoamines and diamines of the benzene and naphthalene series which, moreover, may be subtituted by alkyl, aryl, aralkyl, halogen, hydroxy, acylamino, azo, carboxy and sulfo groups, etc. Illustrative of these are inter alia:

Aminobenzene, 1-arninobenzene-3-sulfonic acid, 1-aminobenzene-4-sulfonic acid,

1-aminobenzene-2-carboxylic acid, 1-aminobenzene-3-carboxylic acid, 1-aminobenzene-4-carboxylic acid, 1-amino-2-methylbenzene, 1-amino-3-methylbenzene, l-amino-4-methylbenzene, 1-amino-2,4-dimethylbenzene, 1-amino-2,5-dimethylbenzene, I-amino-Z-chlorobenzene, l-amino-3-ch1orobenzene, 1-amino-4-chlorobenzene, 1-amino-2,S-dichlorobenzene, 1-amino-2,5-dichlorobenzene-4-sulfonic acid, 1,3-diaminobenzeue, 1,4-diaminobenzene,

i 1,3-diaminobenzene-4-su1fonic acid,

1,4-diaminobenzene-3-sulfonic acid, 1,4-diaminobenzene-3-carboxy1ic acid, 4-acetylamino-l-aminobenzene, 4-carbethoxyamino-l-aminobenzene,

9 4-benzoylamino-l-aminobenzene,

4-amino-1,1-azobenzene,

4,4-diamino- 1, 1'-azobenzene,

4-arnino-4-hydroxy-1,1-azobenzene-3 '-carboxylic acid,

4 amino 4 hydroxy 1,1 azobenzene 3' carboxy 5-sulfonic acid,

1-a1nino-4-hydroxybenzene-3-carboxylic acid,

1amino-3-hydroxybenzene-4-carboxylic acid,

1 amino 4 hydroxybenzene 3 carboxylic acid 5 sulfonic acid,

4,4-diarninodiphenyl,

SOsH

Ha (III) l-aminonaphthalene,

Z-aminonaphthalene,

1-aminonaphthalene-S-sulfonic acid, 1-aminonaphthalene-fi-sulfonic acid, 1-aminonaphthalene-7-sulfonic acid, Z-aminonaphthalene -6-sulfonic acid, 2-aminonaphthalene-3,6-disu1fonic acid,

2-aminonaphthalene-4,8-disulfonic acid,

2-.aminonaphthalene-5,7:-disul-fonic acid, Z-amincnaphthalene-.8-disulfonic acid, l-aminonaphthalene-3,6-di'sulfonic acid, l-aminonaphthalene-3,8-disulionic acid, 1-aminonaphthalene-4,8-disulfonic acid, 1-amino-8-hydroxynaphthalenei-sulfonic acid, Z-amino--hydroxyr1aphthalenb-Z-sulfionic acid, 2-amino-8-hydroxynaphthalene-6rsulfonic acid, 1-amino-8-hydroxynaphthalene-6-sulfonic acid, 1-amino-8-hydroxynaphthalene-2,4-disulfonic acid, 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, 2-amino-8-hydroxynaphthalener3.,6-disulfonic acid, N-monomethylaminobenzene, N-monoethylaminobenzene, N-monobenzylaminobenzene, 1-N-monoethylaminobenzene-3;sulfonic acid, 1-N-monoethylamin,obenzene lrsulfonic acid, Z-methyl-l-N monoethylaminobenzene, 4-methyl-1-N-monoethylaminobenzene, 3-methoxy-l-N-monomemylaminobenzene, 2 N monomethylamino.- 5. hydroxynaphthalene 7 sulfonic acid, 2 N monomethylamino 8 hydroxynaphthalene 6 sulfonic acid, 7

etc. This enumeration is. intended to illustrate the wide variety of derivatives of the benzene andnaphthalene series suitable for reaction with the aforesaid acid chlorides, but is not atall intended to be limitative.

As. coupling components, use may be made of all hydroxybenzene and hydroxynaphthalene compounds which couple in or-tho-position to the azo group. Particularly suitable for this purpose are for example 1,3- dihydroxybenzene derivatives and 4-alkyl-1-hydroxybenzene derivatives, and also hydroxynaphthalene sulfonic acids, and aminohydroxynaphthalene sulfonic acids and their N-substituted derivatives. However, use may be made of all other hydroxynaphtha-lene derivatives hearing substituents which are conventional in azo dyestufis, as for example additional azogroups. As components with couplable methylene groups are. meant primarily acetylacetic acid ar'ylides and 5-pyrazolones, which may moreover contain. substit-uents conventional in these compounds. These components comprise inter alia:

1-acet0acetylaminobenzene, 1-acetoacetylamino-2-methoxybenezene, 1-acetoacetylaminobenzene-3sulfonic acid,

l-acetoacetylaminobenzene-4-sulfonic acid, 1-acetoacetylamino-2-methoxybenzene-x-sulfonic acid, 3-methyl-5-pyrazolone, 1-pheny1-3-methyl-5-pyrazolone,

1- 4'-aminophenyl) -3-methyl-5-pyrazolone,

1-( 3 '-sulfophenyl -3-methyl-5-pyra zolone,

1- (4'-sulfophenyl -3-methyl-5-pyrazolone,

1- 3-carboxyphenyl -3-methyl-5-pyrazolone, 1-phenyl-5-pyraz0lone-3-carboxylic acid, 1-phenyl-5-pyrazoloue-3-carboxylic acid amide,

1- 4-hydroxy-3 '-carb oxyphenyl) -3 -methyl-5 -pyrazolone,

etc. These components withcouplable methylene groups also comprise: barbituric acid, 1,3-indandiene, oxindole, dihydroresorcinol and a, great. many other components, so that the exemplary compounds here enumerated are not at all intended to berestrictivein scope.

Depending upon the selected diazo and coupling components, dyestuffs are obtained. which yield yellow, red, violet, blue and gray to green dyeings on cellulosic fibers. For example, yellow dyestuifs are obtained by coupling diazo compounds from monoamines or diamines of the benzene or diphenyl series with pyrazolones or acetylacetic acid arylides. The same diazo components, when coupled with hydroxynaphthalene derivatives, yield red to violet dyestufis. Red, blue, and green dyestuffs are for example obtained with diazo components derived from naphthalene compounds, for example from 2-(4'-amino- 3' carboxyl 1' benzoylamino). 5 hydroxynapthalene-7-sulfonic acid or 2;-(3-amino-4-carboxy-l'-benzoylamino) -5-hydroxynaphthalene-7-sulfonic acid.

The dyestuffs are suitable for metallization in substance and on the fiber. Metallization in substance can, for example, be carried out with salts of chromium, cobalt, nickel, lead, manganese or copper in neutral or weakly aceLiQ. acid solution or in. sodium acetate metals. Coppering; is preferably eflected inalkaline solution with cop.- per tetraminc complexes. For metallization, on the fiber, the dyeings are aftertreated with salts of bivalent: and polyvalent metals. The metallized dyeings on cellulosic fibers are distinguished by good fas-tness to light and to Washing.

. The following examples set forth representative exemplary embodiments of the invention, and these examples are intended to be solely illustrative and, not at all. limitativc. In these examples, the parts and percentages. are by weight and the temperatures are expressed in degrees. centigrade.

Example I 51 parts of 4,4. di (4" amino 3" carboxybenzoylamino)-diphenyl are dissolved in 70-1) parts, of water with the aid of 8 parts, of sodium hydroxide, and, after. addition 0t 13.8 parts of sodium nitrite, the solution is added dropwise to 55 parts of hydrochloricacid of 30% strength. The tetrazo compound, which separates as a yellow-brown precipitate, is poured at 05 into a solution of 50.8 parts of 1-(4-sulfophenyl)-3-methyl-5- pyrazolone in 200 parts of water and 16 parts of sodium hydroxide, the mixture being then stirred until the coupling is completed, which should be the case after several hours. The resultant dyestuff is precipitated with sodium chloride, isolated and dried. It corresponds to the formula ample. bydissolving. 9.64. parts. of the dyestufi; in,300parts.

of water and; then. stirring, at with 5, partsof. copper sulfate, in presence; of 5 parts of. sodium acetate until the. metal complex is' formed. The complex, is. then pre,.

cipitatedwithsodium chloride, and. is isolated. and, dried. On cotton. and regenerated. ce1lul0se, the ccppen complex. yields thesame; shade as the product; aftercoppered on the.

The nickel complex can be prepared by stirring 9-.64'

parts of the metal-free dyestutf with 5 parts of 'sodium; ac-

date and 5.6 parts" of nickel sulfate in 300 parts of water at 8090 until the metal complex is formed. The thusprepared nickel complex is isolated and also dyes cotton and regenerated cellulose in yellow shades.

In the preparation of the lead complex, 9.64 parts of the metal-free dyestuff are stirred for example with parts of sodium acetate and 6.5 parts of lead acetate in 300 parts of water at 8090 until the metal complex is formed. The complex is then precipitated with sodium chloride, isolated and dried. It also dyes cotton and regenerated cellulose in yellow shades.

To prepare the chromium complex, 9.64 parts of the metal-free dyestutf are stirred for example with 5 parts of sodium acetate and 11.3 parts of chrome alum in 300 parts of water at 80-90 until the metal complex is formed. It dyes cotton and regenerated cellulose in yellow shades.

4,4 di (4" amino 3" carboxy benzoylamino)- diphenyl can be prepared for example by reacting 4,4- diaminodiphenyl with 3-carbomethoxy-4-nitro-l-benzoyl chloride in an organic solvent in the presence of an acidbinding agent. By subsequent saponification of the dicarboxylic acid ester and reduction of the nitro groups, the desired diamino derivatives are obtained.

Similar dyestuffs are obtained when, while otherwise proceeding as hereinbefore described, the 4,4'-di-(4"- amino-3-carboxy-benzoylamino)-diphenyl is replaced by an equivalent quantity of one of the following:

which may be prepared in a manner analogous to that set forth in the preceding paragraph.

- carboxy benzoylamino)- carboxy benzoylamino)- Example 2 69.6 parts of 4,4-di-(4-amino-3"-carboxy-benzoylamino)-stilbene-2,2-disulfonic acid are dissolved in 500 parts of water with the aid of parts of sodium hydroxide and, after addition of 13.8 parts of sodium nitrite, the mixture is added dropwise to 65parts of hydrochloric acid of 30% strength, while cooling. The

tetrazo compound separates out as a yellow-brown precipitate which is then poured, while cooling with ice, into a solution of 25.4 parts of 1-(4'-sulfophenyl)-3- methyl-S-pyrazolone in 12 parts of sodium hydroxide and 100 parts of water. As soon as the coupling component has disappeared, which usually requires only a short time, 17.4 parts of 1-phenyl-3-methyl-5-pyrazolone, dissolved in 100 parts of water and 4 parts of sodium hydroxide, are added. Upon completion of the coupling, the resultant disazo dyestufi is precipitated with sodium chloride and isolated. It corresponds to the formula The new dyestulf is a yellow-brown powder which dissolves in water with yellow coloration. It dyes cotton in light-yellow shades which are converted, upon aftercoppering, into a full yellow which is distinguished by good fastness to light and to washing. The dyestufi, aftercoppered in substance by treatment with copper salts in the presence of sodium acetate at elevated temperature, yields the same shade on cotton as does the product which is aftercoppered on the fiber.

4,4 di (4" amino 3" carboxy benzoylamino)-stilbene-2,2'-disulfonic acid can be prepared for example by reacting 4,4'-diamino-stilbene-2,2-disulfonic acid with 3-carbomethoxy-4-nitro-l-benzoyl chloride in aqueous solution in the presence of an acid-binding agent, whereby the dibenzoylamino compound is formed. The dicarboxylic acid ester is then saponified and the two nitro groups reduced.

Similar dyestuffs, the dyeings of which are however of a somewhat lighter yellow shade, are obtained by following the procedure outlined in the first paragraph of the present example, but replacing the 1-(4-sulfophenyl)-3-methyl-5-pyrazolone by an equivalent quantity of an acetoacetylaminobenzenesulfonic acid, such for example as 1-acetoacetylaminobenzene-3-sulfonic acid, l-acetoacetylaminobenzeneA-sulfonic acid or l-acetoacetylamino-2-methoxybenzene-x sulfonic acid.

Moreover, the 1-phenyl-3-methyl-5-pyrazolone may also be replaced by an equivalent amount of l-acetoacetylaminobenzene or 1-acetoacetylamino-Z-methoxybenzene.

Dyestuifs with similar properties are likewise obtained when, while otherwise proceeding as described in this example, the 4,4 di (4" amino 3 carboxybenzoylamino)-stilbene-2,2disulfonic acid is replaced by an equivalent quantity of one of the following diamines:

1,4-di-(4-amino-3 -carboxy-benzoylamino -benzene,

4,4'-di-(4"-amino-3 "-carboxy-benzoylarnino) -diphenyl,

4,4 di (4" amino 3 carboxy benzoylamino)- 3,3'-dimethoxydiphenyl,

4,4 di (4" amino 3" 3,3-dimethyldiphenyl,

4,4 di (4" amino 3" diphenylurea, etc.

- carboxy-benzoylamino carboxy'-benzoylamino)- Example 3 76.2 parts of the dyestutf of the formula HOaS H03 OOH are dissolved in 100 parts of Water containing 8 parts of sodium hydroxide. After the addition of 6.9 parts of sodium nitrite, the solution is poured slowly, while cooling, into parts of hydrochloric acid of 30% is then coupled with 20.7 parts of l-acetoacetylamino-2- methoxy-benzene, dissolved in parts of water and The new "dyestufl is a yellow-brown powder which dissolves in water with yellow-coloration. It dyes cotton in clear yellow shades which, upon being aftercoppered, are converted into light greenish-yellow of good -fastness to light and to washing. a

'The dyestuff can also be coppered in substance, by

Similar dyestuffs are obtained when, while otherwise proceeding as described in the present example, the coupling component 1-acetoacetylamino-Z-methoxybenl n =on sn-oogmuin-oonsno benzene3-carboxylic acid, 1-acetoacetylaminobenzene-4- carboxylic acid, 1-acetoacetylamino-2-methoxybenzene- X-sulfonic acid, the acetoacetylamino derivative of the formula stirring 11.4 parts of dyestufi with 5 parts of sodium acetate and 5 parts of copper sulfate in 300 parts of water at 80-90 until the metal complex is formed, i whereupon the latter is precipitated with sodium chloride, isolated and dried. 'It dyescotton and regenerated cellulose in the same yellow shades as does the product aftercoppered on the fiber.-

The nickel complex is prepared by stirring -'ll-.4 parts of the metal-free dyestuff with 5 parts of 'sodium acetate and 5.6 parts of nickel sulfatein 300 parts of water at 80 90 until the metal complex is formed. ,It is worked up like the copper complex and also dyes cotton and regenerated cellulose in yellow shades.

The preparation of the cobalt "com'p'lex takes place for example by stirring 11.4 parts "of the metal-free dyestulf with 5 parts of sodium acetate and 5:6 parts barbituric acid, l-phenyl 3-methyl-5-pyrazolone or 1-(3' carboxy-4-hydroxyphenyl)3-methyl-5-pyrazolone.

Thus, by using 1 acetoace'tylaminobenzene 4 carboxylic acid as a coupling component, a dyestuff is obtained, the copper complex compound of which corresponds to the formula of cobalt sulfate in .300 parts of water at 80-90". When and dyes cotton in light greenish-yellow shades of good the complex "compound has been formed, it is precipfastness to light and'washing. itated with sodium chloride, isolated and dried. It Similar dyestuffs are also obtained when, in place dyes cotton and regenerated cellulose in yellow shades. of the dyestu'fi "of Formula IV, the corresponding de- The dyestuff of Formula IV can be prepared for exrivatives substituted in S-position of the nucleus A by a ample by reacting the monoazo dyestuif of the formula sulfonic acid group or in -4-position by the sulfonic acid- (2-carboxypheny1)-amide group:

Granary-c cal e0 5 ILI soin J; 0 on H=OHONH1 H085 (v) O-HN-Ozfl with 3-carbomethoxy-4-nit1'o-l-benzoyl chloride in aque- OOH OOH ous solution in the presence of an acid-binding agent, saponifying the ester and reducing the nitro group to the amino group. are used.

Example 4 saponiiying the ester, and reducing the: nitro group to 84.2 parts of the. dyestufl of the formula the ammo p- HOaSN=NCH-fi-CH;

H=C lEb-QNH- o CQNH:

05H 00011 (VII) are dissolved in 700 parts of water with the aid of 8 Similar dyestuffs are obtained when, while otherwise parts of sodium hydroxide. After the addition of 6.9 parts of sodium nitrite, the solution is poured slowly proceeding as described in. this example, the coupling and while cooling into 45 parts of hydrochloric acid of Component of Formula VI 18 l'ePlaced y the equlvalent strength whereupon a f f 20 quantity of 1-acetoacetylamino-2-methoxybenzene, 1- pound separates out. The suspension is poured into a Solution of parts of the actoacetylamino derivative acetoacetylaminobenzene, 1-acetoacetylammobenzene-4- of Formula VI and 15 parts of sodium hydroxide in carboxylic acid, 1-acetoacetylamino-4-hydroxybenzene-3- 150 Parts of wzltergstirring and cooling being continued carboxylic acid, l-acetoacetylamino-3-hydroxybenzene until the coupling is complete. The resultant dyestufi 25 4 b is precipitated with sodium chloride and isolated. It oxyllc acid, barbltllrlc 36 0r l-phenyl-B-methylcorresponds to the formula 5-pyrazolone.

CH: HOaS- (g0 N\ MagmaC MJJHQHM OH; HO; 10011 0311 The new dyestufi is a yellow-brown powder which dis- Example 5 solves in water with yellow coloration and dyes cotton 50 Parts of the II1011mm dyesfllif 0f the formula in clear yellow shades which, upon aftercoppering, are N N CH -C CH converted into a light greenish-yellow of good fastness H 3 to light and to washing. OOH Q /N The dyestuif of Formula VII can be prepared for ex- N ample by reacting the monoazo dyestufi of the formula H0,s- N=N-cr1c- 0H. c 0 OH I p l coon 0 t NHOCONH \N (IX) are dissolved in 800 parts of water with the aid of 4 parts of sodium hydroxide. After the addition of 6.9

parts of sodium nitrite, the solution is added dropwise HO5S- and While cooling with ice into 30 parts of hydrochloric acid of 30% strength, whereupon a yellow-brown di- H=cH--Nm azo compound separates out. The suspension is poured into a solution of 28.7 parts of 1-acetoacety1amino-2- Hoah (VIII) methoxybenzene-x-sulfonic acid and 12 parts of sodium hydroxide in 100 parts of water, and the mass stirred with 3 cal bomethoxy 4 nitm Lbenzwl chloride; in aque I until coupling is complete. The resultant yellow-brown ant, dyestuff is salted outwith sodium chloride and is then ous solution with the addition of an am 11 mg g Isolated- It corresponds to the formula N coon \N/ CH: COOH I OOH3 SOaH 11 The new dyestuff is a yellow-brown powder which dissolves in water with yellow coloration. It dyes cotton in clear yellow shades which, upon aftercoppering, are converted into a greenish yellow of good fastness to light.

The monoazo dyestufi of Formula IX can be prepared for example by reacting l-(4-aminophenyl)-3- JIOOH proceeding as described in this example, the coupling component 1-acetoacetylamino-2-methoxybenzene-x-sulfonic acid is replaced by an equivalent quantity of lacetoacetylaminobenzene-4-sulfonic acid, l-acetoacetylaminobenzene-4-carboxylic acid, 1-acetoacetylarnino-4- hydroxybenzene-3-carboxylic acid, l-acetoacetylamino- 3-hydroxybenzene-4-carboxylic acid or 1-(4'-sulfophenyl) 58 parts of the monoazo dyestuff of the formula HMS- 4 A N=N-CH-C-CHa e0 1% OOH \N/ are dissolved in 600 parts of water containing 4 parts GQOH 12 After the addition of 6.9 parts of sodium nitrite, the solution is added dropwise and while cooling with ice into 30 parts of hydrochloric acid of 30% strength, whereupon a yellow-brown diof sodium hydroxide.

azo compound separates out. The suspension is poured into a solution of 20.7 parts of l-acetoacetylamino-2- methoxybenzene and 12 parts of sodium hydroxide in 100 parts of water, and the mass stirred until coupling is complete, The resultant yellow-brown dyestufi' is precipitated with sodium chloride and is isolated. It

corresponds to the formula It is a yellow-brown powder which dissolves in water with yellow coloration and dyes cotton in clear yellow shades which, upon aftercoppering, are converted into a light greenish-yellow of good fastness to light and to washing.

The monoazo dyestufi of Formula X can be prepared for example by reacting l-(4-aminophenyl)-3-methyl- S-pyrazolone with 3 -carbomethoxy-4-nitro-l-benzoyl chloride in an organic solvent in the presence of an acid-binding agent. After saponi-fication of the ester and reduction of the nitro. group to amino, the pyrazolone derivative is coupl'e'iil with the diazo= compound from 1-amino-2-carboxybenzene-4=sulfonic acid' to yield the desired monoazo dyestutf,

Similar dyestufts: result when while other proceeding as described in this example, the monoazo dyestuff of Formula X is replaced by the equivalent quantity of the corresponding dyestufi which contains the sulfonic acid group in 5-position of nucleus A instead of in the 4-position or of the dyestufi wherein the 4-positioned sulfonic acid group is replaced by the sulfonic acid-(2-carboxyphenyl)-amide group.

In the latter case, a dyestuft is obtained which corresponds to the formula COOH OCH:

Similar dyestuffs are likewise obtained when, while otherwise proceeding as described in this example, the coupling component 1-acetoacetylamino-Z-methoxybenzene is replaced by an equivalent quantity of l-acetoacetylaminobenzene, barbituric acid, l-phenyl-S-methyl- -pyrazolone or the acetoacetylamino derivative of Formula VI.

Example 7 100.2 parts of the azo dyestuff of the formula OH (|)H H30 0 0 CH3 OH HOaS- SOaH HO S- OH OH H30 0 O CH: OH

SOaH- SOaH HOaS The copper complex of the dyestuif is obtained by stirring the dyestulf, thus isolated, with a solution of 47.5 parts of copper sulfate and 127 parts of aqueous am- Nat-O0 O-HN sonar 08s monia of strength in 3000 parts of water at i4 Dyestutfs with similar properties are obtained when, while otherwise proceeding as described in this example, the coupling component 1,8-dihydroxynaphthalene- 3,6-disulfonic acid in the starting dyestuif is replaced by l-hydroxynaphthalene-3,6-disulfonic acid, l-hydroxynaphthalene-3,8-disulfonic acid, or 1-hydr0xynaphthalene-3,6,8-trisulfonic acid.

By replacing the 2-(3'-amino-4'-carbomethoxy-l'-benzoylamino)-5-hydroxynaphthalene-7-sulfonic acid by 2- (3' carbomethoxy 4' amino 1 benzoylamino) 5 hydroxynaphthalene-7-sulfonic acid, a greenish-blue dye- OOOOH:

stuff is obtained, while if it is replaced by 2-(3'-amino- 4 carbomethoxy 1 N methyl benzoylamino) S-hydroxynaphthalene-7-sulfonic acid or 2-(3'-amino- 4 carbomethoxy 1 N ethyl benzoylamino) 5 hydroxynaphthalene-7-sulfonic acid, blue-gray dyestuffs are produced.

If, as coupling component, the l-acetoacetylaminobenzene is replaced by 1-pheny1-3-methyl-5-pyrazolone, blue-gray dyestuffs result, while if it is replaced by 2- hydroxynaphthalene, the products dye cotton in marineblue shades.

CH: COUCH: (I20 NH-OO- N=N-dH-oo-HN- Example 8 109.8 parts of the azo dyestufi of the formula 0on5 OH are dissolved in 4000 parts of water, 6.9 parts of so- 80-100 until the copper complex forms, which is the dium nitrite added, and the solution poured into 50 case after about 15 hours. It corresponds to the formula amino-S-hydroxynaphthalene-7-sulfonic acid and 3-nitro-4-carbomethoxy-1-benzoyl chloride in aqueous solution in the presence of an acid-binding agent, followed by reduction of the nitro group to amino.

parts of hydrochloric acid of 30% strength, while cool- CHa ing. The suspension, containing the tetrazo compound as a dark precipitate, is poured into a solution of 50.8 parts of l-(4-sulfophenyl)-3-methyl-5-pyrazolone and 24 parts of sodium hydroxide in 200 parts of water, and

the mass stirred and cooled with ice until coupling is complete. 80-100 in a solution of 62.5 parts of copper sulfate and 170 parts of aqueous ammonia of 25% strength out with sodium chloride and isolated.

The dyestutf, after isolation, is. heated to H The uncoppered dyestufi corresponds to the formula \N/ cnaood 03H It is a dark powder which dissolves in water with gray coloration. It dyes cotton in neutral gray shades of good fastness properties.

The aforementioned dyestuif of Formula XII can be prepared by coupling l mol of t'etrazotized 3,3'-dimethoxy-4,4'-diaminodiphenyl with 2 mols of 2-(3--carbomethoxy 4' amino 1' benzoylamino) 5 hydroxynaphthalene-7-sulfonic acid. The latter is obtained by the reaction, in aqueous solution, of Z-arnino-S-hydroxynaphtha1ene-7-sulfonic acid with 3-carbomethoxy-4-nitro-l benzoyl chloride in the presence of an. acid-binding agent, followed by the reduction of the nitro group of the thus-produced intermediate to the amino group. By replacing the '2-(3"-carbomethoXy-4-amino-'lf-benzoylamino)-5hydroxynaphthalene-7sulfonic acid by 2-(3- amino 4 carbomethoxy 1 benzoylarnino) 5 hydroXynaphtha1ene-7-sulfonic acid, a dyestufi of similar properties is obtained.

Similar dyestuffs are likewise obtained if the coupling component 1-(4'-sulfophenyl)3-methyl-5-pyrazolone is replaced by I-(3' carboxy-4'-hydroxyphenyl)-3'- methyl-S-pyrazolone or by l-acetoacetylamino-Z-methoxybenzene-x-sulfonic acid.

Similar dyestuffs are also obtained when, in the starting compound of Formula XII, the hydrogen atom designated by is replaced by a methyl or ethyl group.

Example 9 27 parts of 3-carboxy-4-aminobenzene-l-carboxylic acid-phenylamide and 4 parts of sodium hydroxide are dissolved in 200 parts of water, 6.9 parts of sodium nitrite added, and the solution poured into 30 parts of hydrochloric acid of 30% strength. The resultant brown suspension of diazo' compound is admixed with a solution of 26.6- parts of the dipyrazolone' of the formula in 4 parts of sodium hydroxide, parts of sodium carbonate and: 200; parts of water, and the mass is stirred at 0-5 until the dyestufi formation is complete, which requires several hours. The dyestuif is precipitated with sodium chloride, and is isolated and dried. It corresponds to' the formula solves in water with yellow coloration, and dyes cotton and regenerated cellulose in light yellow shades. Upon aftercoppering, the color of the dyeings changes to a full yellow which is characterized by good fastness to light and washing.

3carboxy-4-aminobenzene-l-carboxylic acid-phenylamide can be prepared for example by reacting aminobenzene with 4-nitro-3-carbomethoxy-l-benzoyl chloride ,in an organic solvent in the presence of anhydrous sodium acetate. By saponifying the carboxylic acid ester and reducing the nitro-group to amino, the desired amino compound is obtained.

Similar dyestuffs are obtained when, While otherwise proceeding as described in this example, the 3-carboXy- 4=aminobenzene-l-carboxylic acid-phenylamide is replaced by an equivalent quantity of 3-carboXy-4-arninobenzene-l-ca'rboxylic acid-N-methyI-phenylamide, 3-carboxy-4-aminobenzene l-carboxylic acid-N e'thyl-phenylamide, 3-carboxy-4-aminobenzene-l-carboxylic acid-dip'henylamide or 3-carboxy-4-aminobenzene-l-carboxylic acid-'(2'-, 3"- or 4-methyl)-phenylamide.

Example 10 1 part of the first d'yestufi according to Example 4 is dissolved in water and is added to a porcelain receptacle containing 2000 parts of water and 10 parts of sodium sulfate. parts of cotton cloth are introduced into thisbath at and the temperature then raised to 90'100 with frequent movement of the material. When, after about one hour, the dye has drawn onto the fabric, the temperature is allowed to drop. If aftercoppering is desired, the light yellow dyed material is introduced into a bath at 60 containing a solution I of 5 parts of copper sulfate and 1 part of acetic acid in 2000 parts of water. The material is manipulated in this bath for 30' minutes, after which it is rinsed with water.

Having thus disclosed the invention what claimed is: 1. An azo dyestuff which corresponds to the formula wherein each of m and n is one of the integers 1 and 2,

R stands-when m is lfor a member selected from the group consisting of mononuclear radicals of the benzene series and binuclear radicals of the benzene series wherein the benzene nuclei are connected by a bridge selected from the group consisting of the simple 17 diphenyl linkage, -CH=CH, -NH-CO- an -NH-CO-NH, and-when m is 2-for a member selected from the group consisting of radicals of the, pyrazolone series and the naphthalene series, R stands for a member selected from the group consisting of 5 monoand binuclear radicals of the benzene series, one T stands for the residue of an azo component selected -from the group consisting of residues of the pyrazolone and the acetoacetylaminobenzene series, barbituric acid and of hydroxybenzenes and hydroxynaphthalenes cou- 10 pled in ortho-position to the hydroxygroup, and the other T stands for a member selected from thegroup consisting of -COOH and -COO-lower alkyl, Z stands for a member selected from the group consisting of hydrogen, lower alkyl and radicals of the benzene 15 series, Q stands for a member selected from the group consisting of a residue of an azo component of the naphthalene 'series'and of a substituent corresponding to the formula Me stands for a heavy metal atom selected from the group consisting of chromium, manganese, cobalt, nickel, copper and lead atoms, and m is one of the integers 1 to 7. p

2. An azo dyestufi according to claim 1, wherein the heavy metal atom is copper.

3. The azo-dyestulf corresponding to the formula HOaS- 4. The azo dyestufi corresponding to the formula OOOH OCH:

OH: to

5. The azo dyestuif corresponding to the formula HOaS C O OH (I) O CE! 6. The azo dyestufi corresponding to the formula 19 20 7. The azo dyestuff corresponding to the formula.

HO O--( 3u--O 0 2 911-0 v l l MILO N=1 T O CH! som- SO|H HO;S-- NliCo-g O Clw-O References Cited in the file of this patent UNITED STATES PATENTS 2,218,299 Schmid .......Q Oct. 15, 1940 2,306,681 Zerweck et a1. Dec. 29, 1942 2,507,754 Bossard et a1 May 16, 1950 

7. THE AZO DYESTUFF CORRESPONDING TO THE FORMULA 